JP2000194295A - Reversible and thermally color changing display body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reversible thermally color changing display body which displays various different images by temp. changes and which contributes to color changes, unexpected display, magical appearance, and various designs. SOLUTION: This reversible thermally color changing display body 1 has a thermally color changing image (A), thermally color changing image (B) and non-thermally color changing image (C) on a supporting body 2. The image (A) contains reversible thermally color changing pigments which develop colors from an color erased state by heating and which erase their colors when temp. is decreased from the color developing state. The image (B) contains reversible thermally color changing pigments which erase the colors by heating from a color developing state and develop colors by cooling from the color erased state.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a reversible thermochromic display. More specifically, the present invention relates to a reversible thermochromic display in a printing form or a plastic molded body form in which a thermochromic material of a heat coloring type and a thermochromic material of a heat decoloring type coexist.

[0002]

2. Description of the Related Art Conventionally, heat discoloration type thermochromic materials,
That is, a reversible thermochromic material that is decolorized by heating from a color-developed state and colored by cooling from a decolorized state is a thermochromic printing field, a toy field, and the like, which has a thermodynamic effect, a taste due to a color change, and a surprising taste. It is applied to impart properties, magic and the like. In the printing field, in order to effectively develop a color change effect, a concealment print layer that covers the non-thermochromic image of the base is formed with the reversible thermochromic material, and the concealment print layer is decolored by heating, and is heated at room temperature. In the region, a printing method having a configuration in which a non-thermochromic image in an invisible state is revealed is adopted, and is widely used in picture books, drinking cups, and the like. Further, the reversible thermochromic material is integrally blended into a thermoplastic, and is applied as a toy-shaped object to impart a color changing effect. On the other hand, several proposals have been disclosed for a thermochromic material of a heat coloring type, that is, a reversible thermochromic material that develops a color by heating from a decolored state and decolors by cooling from a colored state. However, as described above, they are not practical in the printing field, the toy field, and the like. For example, an attempt to utilize the temperature dependence of the acid dissociation property of an acidic phosphate compound (Japanese Patent Publication No. 23592/1990) is disclosed. However, the coloring density is insufficient, and It is difficult to microencapsulate the discolorable composition containing the ester compound, and the durability is not satisfied. In the heat-sensitive recording material field, a heat-coloring type recording material (for example, JP-A-5-124360)
However, the color is developed by applying a temperature of more than one hundred and several tens of degrees by a thermal head or the like of a thermal printing apparatus, and the color is not developed by a heating means in a living environment temperature range. The application to the field, toy field, etc. is not satisfied.

[0003]

SUMMARY OF THE INVENTION The inventor of the present invention has made intensive studies on a thermochromic material of a heat-coloring type which develops a color by heating means in a living environment temperature range.
No. 6294, "Reversible thermochromic composition". The present invention provides a heat discoloration-type thermochromic material, which is used in combination with a conventional heat discoloration-type thermochromic material. Compared to discolored printed matter and thermo-discolored modeling toys, etc.
The purpose of the present invention is to develop a remarkable thermal discoloration effect rich in the exquisiteness, unexpectedness, magic and the like of discoloration, and to effectively apply it to a printing field, a toy field, and the like. This will be described below. In the above-mentioned concealed printed matter made of a conventional heat decoloring type thermochromic material (a structure in which the color is concealed at room temperature and the base is exposed by heat decoloration), in order to effectively exhibit the concealing effect. In the concealment printing layer, the color tone at the time of color development is inevitably configured to be similar to the color of the non-thermochromic image of the base, or to a dark color. Since the appearance is specified by the location of the concealed printing layer, the discoloration taste, unexpectedness, magic effect, and the like are not necessarily satisfied. According to the present invention, by applying a thermochromic material of a heat coloring type, a color image can be suddenly brought out from an invisible state in a normal temperature range, and the above-mentioned problem can be solved. Combined use with the thermochromic material of the mold, the widening of the discoloration temperature range makes it possible to alternately hide and reveal images at temperatures above or below normal temperature range, significantly improving the discoloration effect and diversifying the design. It is an object of the present invention to provide a reversible thermochromic display which is extremely effective in the field of thermochromic printing as described above and further in the field of plastic toys by blending the thermochromic materials. .

[0004]

According to the present invention, there is provided a thermochromic image A containing a reversible thermochromic pigment a which forms a color by heating from a decolored state and is decolored by a decrease in temperature from the colored state; The support 2 is provided with a thermochromic image B containing a reversible thermochromic pigment b which is decolorized by heating and which develops a color by cooling from the decolored state.
The reversible thermochromic display 1 coexisting on the above is a requirement. Further, the thermochromic image A and the thermochromic image B are juxtaposed or partially or wholly in the overprinted state, the non-thermochromic image C is provided, the thermochromic image A, the thermochromic image B And the non-thermochromic image C are all print images, and the reversible thermochromic pigments a and b are blended to form a thermochromic mixed image. Furthermore, a reversible thermochromic pigment a that develops color by heating from the decolored state and decolorizes by lowering the temperature from the colored state, and decolorizes by heating from the colored state,
Reversible thermochromic pigment b that develops color upon cooling from the decolored state b
Are mixed and fixed in a dispersed state in a resin molded body. Further, in the normal temperature range (10 to 35 ° C.), the reversible thermochromic pigment a is in a decolored state, the reversible thermochromic pigment b is in a color-developed state, and decolored by heating from the color-developed state. A reversible thermochromic image B having a discoloration temperature different from that of the reversible thermochromic pigment b, which is colored by cooling from a color state, and containing a reversible thermochromic pigment b ′ in a decolored state in a normal temperature range (20 to 35 ° C.) 'Or blended with a reversible thermochromic pigment b'. Further, the reversible thermochromic pigment a is
(A) an electron-donating color-forming organic compound, (b) an electron-accepting compound selected from an alkoxyphenol compound represented by the following general formula (1) or a hydroxybenzoic acid ester compound represented by the following general formula (2), C) The above (a),
It is required that the pigment is a microcapsule pigment in which three essential components comprising a reaction medium for reversibly causing the electron transfer reaction according to (b) are encapsulated in microcapsules.

[0005] The reversible thermochromic pigments b include conventional heat-decolorable thermochromic materials such as (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, And (c) a homogeneous solution containing three components of a reaction medium for determining the temperature at which the color reaction of both occurs.
A form in which a known reversible thermochromic composition is encapsulated in a microcapsule is effective. Specifically, Japanese Patent Publication No. 51-44706 and Japanese Patent Publication No.
No. 1-444708, Japanese Patent Publication No. 1-29898,
Those described in Japanese Patent Publication No. 4-17154 can be used. Further, JP-A-6-1067 and JP-A-6-16-1
068, JP-A-6-8628 and the like,
A thermochromic material showing a metallic gloss color change such as gold, silver or metallic color can be applied.

As the reversible thermochromic pigment a, those obtained by encapsulating a heat-colorable reversible thermochromic composition described in Japanese Patent Application No. 9-316294 previously proposed by the present applicant in microcapsules are particularly preferable. It is valid. The heat-colorable reversible thermochromic composition comprises (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reaction for determining a temperature at which a color reaction between the two occurs. In the composition containing the essential three components of the medium, as the component (b), the alkoxyphenol compound represented by the general formula (1) or the general formula (2)
By applying the hydroxybenzoic acid ester represented by the formula, unlike the discoloration behavior of the conventional heat-decoloring type thermochromic material (see FIG. 2), the color is formed by heating from the decolored state, and FIG. 1 shows the discoloration behavior (FIG. 1) in which the color is erased by lowering the temperature.

As the component (a), conventionally known diphenylmethanephthalides, phenylindrylphthalides, indolylphthalides, diphenylmethaneazaphthalides, phenylindrylazaphthalides, fluorans, Stilinoquinolines, diaza rhodamine lactones and the like can be applied.

The following are examples of the alkoxyphenol compound effective as the component (b). pn-propyloxyphenol, pn-butyloxyphenol, p
-N-pentyloxyphenol, pn-hexyloxyphenol, pn-heptyloxyphenol,
pn-octyloxyphenol, pn-nonyloxyphenol, pn-decyloxyphenol, p
-N-undecyloxyphenol, pn-dodecyloxyphenol, pn-tridecyloxyphenol, pn-tetradecyloxyphenol, pn-
Pentyldecylphenol, pn-hexyldecyloxyphenol, pn-heptyldecyloxyphenol, pn-oxydecylphenol, pn-heptyloxyphenol, pn-octyldecylphenol, p-isopropyloxy Phenol, p-1-methylpropyloxyphenol, p-3-methylbutyloxyphenol, p-2-methylpentyloxyphenol, p-1-ethylpentyloxyphenol, p
-1-ethylhexyloxyphenol, p-3, 5,
5-trimethylhexyloxyphenol, p-3,7
-Dimethyloctyloxyphenol, p-1-ethylpropyloxyphenol, p-2-methylhexyloxyphenol, p-1-methylheptyloxyphenol, p-1-methyloctyloxyphenol and the like. The alkoxyphenol compound, the larger the number of carbon atoms in the straight-chain alkyl group, the smaller the temperature difference between the melting point and the cloud point, the higher the crystallinity tends to be. It can be used at the discoloration temperature.

The following are examples of hydroxybenzoic acid esters effective as the component (b). 3-hydroxybenzoic acid tridecyl ester, 3-hydroxybenzoic acid tetradecyl ester, 3-hydroxybenzoic acid pentadecyl ester, 3-hydroxybenzoic acid hexadecyl ester, 3-hydroxybenzoic acid heptadecyl ester,
Octadecyl 3-hydroxybenzoate, nonadecyl 3-hydroxybenzoate, eicosyl 3-hydroxybenzoate, heneicosyl 3-hydroxybenzoate, docosyl 3-hydroxybenzoate, 4-hydroxybenzoic acid Tridecyl ester, 4-hydroxybenzoic acid tetradecyl ester,
Pentadecyl 4-hydroxybenzoate, hexadecyl 4-hydroxybenzoate, heptadecyl 4-hydroxybenzoate, octadecyl 4-hydroxybenzoate, nonadecyl 4-hydroxybenzoate, eico 4-hydroxybenzoate Sil ester, 4-hydroxybenzoic acid heneicosyl ester, 4-hydroxybenzoic acid docosyl ester, 3,
4-dihydroxybenzoic acid tridecyl ester, 3,4
Tetradecyl dihydroxybenzoate, 3,4
Pentadecyl dihydroxybenzoate, 3,4
Hexadecyl dihydroxybenzoate, 3,4
Heptadecyl dihydroxybenzoate, 3,4
Octadecyl dihydroxybenzoate, 3,4
Nonadecyl dihydroxybenzoate, 3,4-
Eicosyl dihydroxybenzoate, 3,4-dihydroxybenzoic acid eicosyl ester, 3,4-dihydroxybenzoic acid
Docosyl dihydroxybenzoate, tridecyl 3,5-dihydroxybenzoate, tetradecyl 3,5-dihydroxybenzoate, pentadecyl 3,5-dihydroxybenzoate, hexadecyl 3,5-dihydroxybenzoate Heptadecyl 3,5-dihydroxybenzoate, octadecyl 3,5-dihydroxybenzoate, nonadecyl 3,5-dihydroxybenzoate, eicosyl 3,5-dihydroxybenzoate, 3,5-dihydroxybenzoate Acid eicosyl ester, docosyl 3,5-dihydroxybenzoate The alkyl group of the compound is a straight-chain or side-chain alkyl group having 13 to 22 carbon atoms. A system having an alkyl group having less than 13 or more than 22 carbon atoms does not satisfy practicality due to low crystallinity. In consideration of more practical performance such as discoloration characteristics and color density, the alkyl group of the compound is more preferably a straight-chain alkyl group having 14 to 20 carbon atoms.

The above two components (a) and (b)
The composition comprising the components also exhibits reversible color development, but the adjustment of the discoloration temperature is limited, and the use of the component (c) makes the adjustment of the discoloration temperature practical. As the component (c), conventional reaction media such as hydrocarbons, halogenated hydrocarbons, sulfides, ethers, ketones, esters, acid amides, alcohols, and waxes are all effective. And, like medium molecular weight polymers,
It may be a semi-liquid substance, and one or more of these compounds can be applied. By selecting the compound of the component (c), a hysteresis characteristic is obtained in which a curve from the decolored state to the color-developed state and a path from the color-developed state to the decolored state are greatly different from each other in a curve plotting the change in the coloring density due to the temperature change. be able to.

The interaction between the components (a), (b) and (c) will be described. Among the components (b), the alkoxyphenol compound has a relatively low melting point, a small difference between the melting point and the cloud point, and has characteristics that are rich in crystallinity. In a melting state or a dissolved state, a color-developed state is generated by an electron transfer reaction with the component (a), and in a cooling process from the color-developed state, the alkoxyphenol compound is crystallized and separated from the component (a), It is presumed that a discolored state is formed, and the discoloration temperature can be set by selecting an alkoxyphenol compound having an appropriate melting point and cloud point. The color change characteristics of the reversible thermochromic composition in which the three components (a), (b) and (c) are homogeneously mixed will be described with reference to a graph showing a color density-temperature curve in FIG.
The change in the color density due to the temperature change proceeds along the arrow.
Here, T ₁ indicates a color development start temperature, T ₂ indicates a complete color development temperature, T ₃ indicates a decolorization start temperature, and T ₄ indicates a complete decoloration temperature. The hysteresis width ΔH is calculated from the following equation as the temperature difference between the path from the decolored state to the colored state and the path from the decolored state to the colored state. _{ΔH = (T 2 -T 1)} / 2- (T 3 -T 4) / 2 Therefore, the composition for forming a colorless state by T ₁ following the temperature begins to color than the temperature of T ₁ in the heating process , T ₂
Upon reaching the temperature becomes full colored state, when heated to temperatures above T _2, in the process of cooling to reach a temperature of T ₃ starts to decoloring, thinner color density when further cooled to a temperature T ₄ completely decolorized reached, the composition was cooled to a temperature below T ₄ reversibly to reproduce the discolouration behavior.

The reversible thermochromic pigment a composed of a capsule containing the reversible thermochromic composition has the same color-changing properties as described above. Incidentally, microencapsulation is conventionally known interfacial polymerization method, in situ polymerization method, in-liquid curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent,
A melt dispersion cooling method, an air suspension coating method, a spray drying method and the like are appropriately selected. Furthermore, a secondary resin film may be provided on the surface of the microcapsule according to the purpose to impart durability, or the surface characteristics may be modified for practical use. By microencapsulating into a pigment form, even if it comes into contact with a chemically active substance such as an acidic substance, a basic substance, or a peroxide, or a solvent component, of course, its function is not reduced. This is because the heat-resistant stability can be maintained, and the reversible thermochromic composition is maintained under the same composition under the various use conditions, and can exert the same effect, and has a particle diameter of 1 to 50 μm. Preferably, a pigment in the form of a micro couple having a size of about 3 to 30 μm is more effective in terms of dispersibility, color development, durability and processability.

Thermochromic image A and thermochromic image B in the present invention
Is a thermochromic image in which the above-described reversible thermochromic pigments a and b are fixed in a dispersed state in a binder resin, and is formed on the support 2 by printing or spraying. The thermochromic images (A, B) are prepared by using a conventional binder resin, for example, a vehicle containing a resin selected from various synthetic resin emulsions, water-soluble or oil-based synthetic resins, ultraviolet curable resins, and other adhesives. As a printing ink or paint in which the reversible thermochromic pigments a and b are respectively dispersed, the amount of adhesion to a desired portion of a target support by a conventionally known printing means such as screen printing or gravure printing, or a means such as spray coating. , And an appropriate amount is applied and dried. The reversible thermochromic pigment (a, b) accounts for 5 to 85% by weight (preferably 10 to 60%) in the thermochromic image.
% By weight). If it is less than 5% by weight, the color density is low,
When the color change is not clearly visible, on the other hand, when it exceeds 85% by weight, there is a residual color at the time of decoloration, and further, the fixing strength is not practical. The thickness of the thermochromic image is practically in the range of 3 μm to 400 μm, preferably 10 μm to 200 μm. When the thickness is 3 μm or less, the color change lacks sharpness.
If the thickness exceeds 0 μm, the appearance is likely to be impaired.

The non-thermochromic image C is a printing ink or paint in which a conventionally known dye, general pigment, fluorescent pigment, luminous pigment, luminous pigment, metal powder, pearl pigment, or the like is dispersed in a vehicle containing a binder resin. By known coating means such as printing or spraying.

A molded article obtained by resin molding is prepared by blending 0.1 to 40% by weight (preferably 0.2 to 25% by weight) of reversible thermochromic pigments a and b in a thermoplastic resin. A molding having a desired shape is formed by the molding means.

Further, in the present invention, in a display system in which the reversible thermochromic pigment b shows a decolored state in a normal temperature range, the color is decolored by heating from the colored state, and is colored by cooling from the decolored state. A reversible thermochromic pigment B ′ having a discoloration temperature different from that of the reversible thermochromic pigment b, and including the reversible thermochromic pigment b ′ in a decolored state at room temperature, or
By blending and using the reversible thermochromic pigment b ′ together with the reversible thermochromic pigments a and b, a display material with more excellent color change can be obtained.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The reversible thermochromic display of the present invention is a reversible thermochromic image A, B formed by printing or coating and, if necessary, coexisting with a thermochromic image B '. The thermochromic pigments a and b, and if necessary, b 'may be mixed and fixed in a molding resin in a dispersed state.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Reversible thermochromic pigment a used in the present invention a
Are listed in Table 1, and the reversible thermochromic compositions constituting the reversible thermochromic compositions b and b 'are shown in Table 2, respectively. The reversible thermochromic pigments a, b, and b ′ are pigments obtained by enclosing the reversible thermochromic composition in microcapsules, respectively. The numbers in parentheses in the table indicate parts by weight.

[0019]

[Table 1]

[0020]

[Table 2]

Example 1 Preparation of reversible thermochromic pigment [(a) -1] 3- [2-ethoxy-4- (N-ethylanilino) phenyl] -3- (1-ethyl-2-methylindole-3
-Yl) -4-azaphthalide 1.5 parts by weight, pn-decyloxyphenol 10.0 parts by weight, n-docosan 3
0.0 parts by weight, 2- (3-t-butyl-5-methyl-2)
-Hydroxyphenyl) -5-chlorobenzotriazole was heated and dissolved at 120 ° C. at a temperature of 120 ° C. to obtain a homogeneous reversible thermochromic composition (1).
(Epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd.) 10
After mixing with the mixed solution in parts by weight, the mixture is dropped into 100 parts by weight of a 10% gelatin solution, and the mixture is stirred so as to be fine droplets. 5.0 parts by weight of curing agent Epicure U separately prepared
A solution obtained by dissolving (an amine adduct of an epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.) in 45.0 parts by weight of water was gradually dropped into the stirring solution, and the liquid temperature was maintained at 80 ° C. The stirring was continued for about 5 hours to obtain a microcapsule stock solution. Further, a reversible thermochromic pigment [(a) -1] obtained by microencapsulating the stock solution by centrifugation.
I got The reversible thermochromic pigment [(a) -1] is shown in FIG.
As shown in FIG. At room temperature, it is in a decolorized state (colorless). When heating is started, color starts to be formed from around 45 ° C. (T ₁ ), and at 60 ° C., a blue color is formed (T ₂ ). The color development state is maintained until (T ₃ ), and the color is gradually erased by further cooling to a completely erased state (T ₄ ) at 28 ° C.

Preparation of Reversible Thermochromic Pigment [(b) -1] A reversible thermochromic pigment [(b) was prepared in the same manner as in Example 1 except that the reversible thermochromic composition (11) was used. )
-1] was obtained. The reversible thermochromic pigment [(b) -1]
Is a heat decoloring type, and exhibits a discoloration behavior of developing color upon cooling (see FIG. 2). Below 37 ° C, it develops blue color and 4
At 0 ° C. or higher, the colorless (colorless) state is exhibited.

Preparation of Ink 40.0 parts by weight of the reversible thermochromic pigment [(a) -1] was added to 60.0 parts by weight of a hard epoxy resin, and an ultraviolet absorber 2.0
Parts by weight, a thixotropic agent 2.0 parts by weight, and an antifoaming agent 1.0
After uniformly dispersing and kneading in a vehicle containing parts by weight, 35.0 parts by weight of a room temperature-curable aliphatic polyamine was added and uniformly dispersed and kneaded to obtain a heat-colorable epoxy ink. In addition, using the reversible thermochromic pigment [(b) -1], an ink was formed in the same manner as described above to obtain a heat-erasable epoxy ink.

Preparation of a reversible thermochromic display body On the side of a ceramic mug, approximately the lower half of the egg pattern was printed with a curved surface printing machine using a blue epoxy ink.
C. for 1 hour to obtain a non-thermochromic image C. Next, a pattern of the upper body of the dinosaur was printed on the upper half of the pattern of the egg using the heat-coloring type epoxy ink, and was heated and cured at 70 ° C. for 1 hour to obtain a thermochromic image A. Furthermore, on both sides of the dinosaur pattern using the heating coloring type epoxy ink,
A part of the pattern in which the egg in the upper half was cracked was printed, and was heated and cured at 70 ° C. for 1 hour to form a reversible thermochromic image A. Then
Overprint the upper half of the egg pattern on the dinosaur's upper body pattern (reversible thermochromic image A) using a heat-decolorable epoxy ink, heat and cure at 70 ° C for 1 hour to obtain a reversible thermochromic image B Formed to obtain a reversible thermochromic mug. In the reversible thermochromic mug, the reversible thermochromic image A is not visible in a room temperature environment, and the egg pattern by the non-thermochromic image C and the reversible thermochromic image B is visible. When hot water of 70 ° C. is poured into the mug, the reversible thermochromic image B is erased and the reversible thermochromic image A is colored, so that an image in which the egg is broken and a dinosaur is born appears. Next, when hot water is taken out and the mug is left in a room temperature environment, the original state is restored again. The change in appearance before and after the discoloration is shown in FIGS. This change could be repeatedly reproduced by the temperature change.

Example 2 Preparation of reversible thermochromic pigment [(a) -2] A reversible thermochromic pigment [((a) -2] was prepared in the same manner as in Example 1 except that the reversible thermochromic composition (2) was used. a) -2] obtained. The reversible thermochromic pigment [(a) -2] is a heat-colorable pigment, exhibits a discoloration behavior as shown in FIG. 1, is in a decolored state (colorless) in a normal temperature range, and becomes 44 when heated. The color starts to develop from around ℃ (T ₁ ), becomes a magenta color development state at 51 ° C. (T ₂ ), and then, when cooling is started, the color development state is maintained up to 35 ° C. (T ₃ ), and gradually cooled by further cooling The color is completely erased at 28 ° C. (T ₄ ).

Preparation of Reversible Thermochromic Pigment [(b) -2] A reversible thermochromic pigment [(b) -2] was prepared in the same manner as in Example 1 except that the reversible thermochromic composition (12) was used. 2]
I got The reversible thermochromic pigment [(b) -2] is a heat-decoloring type, exhibits a discoloration behavior that develops color upon cooling (see FIG. 2), and develops a bluish green color at 37 ° C. or lower (t ₁ ),
At 40 ° C. or higher (t ₂ ), it exhibits a decolored (colorless) state.

Preparation of Ink 40.0 parts by weight of the reversible thermochromic pigment [(a) -2] was added to 60.0 parts by weight of a hard epoxy resin and an ultraviolet absorber 2.0
After uniformly dispersing and kneading in a vehicle consisting of 2.0 parts by weight of a thixotropic agent and 1.0 part by weight of an antifoaming agent, 35.0 parts by weight of a room temperature-curable aliphatic polyamine is added. The mixture was dispersed and kneaded to obtain a heat-colorable epoxy ink. Also,
Using a reversible thermochromic pigment [(b) -2], an ink was obtained in the same manner as described above to obtain a heat-decolorable epoxy ink.

Preparation of a reversible thermochromic display body A tree branch pattern was printed on a side surface of a plastic cup using a brown epoxy ink with a curved printing machine as a support, and was heated and cured at 70 ° C. for 1 hour. A thermochromic image C was formed. Next, using the heating decolorable epoxy ink,
A pattern of butterfly pupae is overprinted on the non-thermochromic image C and heat-cured at 70 ° C. for 1 hour to form a reversible thermochromic image B. Was overprinted and heat-cured at 70 ° C. for 1 hour to form a reversible thermochromic image A to obtain a reversible thermochromic plastic cup.

The reversible thermochromic plastic cup is
Under the room temperature environment, the reversible thermochromic image A is not visible, and the pattern of the tree branch and the butterfly pupa by the non-thermochromic image C and the reversible thermochromic image B is visible. When hot water of 60 ° C. is poured into the plastic cup, the reversible thermochromic image B is erased, the reversible thermochromic image A is colored, and a pattern transformed from a pupa to a butterfly appears. Next, take out the hot water and leave the plastic cup in a room temperature environment to return to the original design again. Incidentally, the above-mentioned aspect change is repeatedly reproduced by a temperature change.

Example 3 Preparation of Reversible Thermochromic Pigment [(a) -3] A reversible thermochromic pigment [[a] -3] was prepared in the same manner as in Example 1 except that the reversible thermochromic composition (3) was used. (A) -3]
I got The reversible thermochromic pigment [(a) -3] is a heat-colorable pigment, exhibits a discoloration behavior as shown in FIG. 1, is in a decolored state (colorless) in a normal temperature range, and becomes 45% when heating is started. ° C
Coloring starts near (T ₁ ), changes to a pink color developing state at 60 ° C. (T ₂ ), and when cooling is started, the color developing state is maintained up to 35 ° C. (T ₃ ) and gradually cooled to further cool down. The color is erased and completely erased at 28 ° C. (T ₄ ).

Preparation of Ink 40.0 parts by weight of the reversible thermochromic pigment [(a) -3] was added to 60.0 parts by weight of a hard epoxy resin, and an ultraviolet absorber 2.0
After uniformly dispersing and kneading in a vehicle consisting of 2.0 parts by weight of a thixotropic agent and 1.0 part by weight of an antifoaming agent, 35.0 parts by weight of a room temperature-curable aliphatic polyamine is added. The mixture was dispersed and kneaded to obtain a heat-colorable epoxy ink. Also,
Using a reversible thermochromic pigment [(b) -2], an ink was obtained in the same manner as described above to obtain a heat-decolorable epoxy ink.

Fabrication of a reversible thermochromic display body A tree pattern was printed on the side surface of a ceramic mug with a curved surface printing machine using a brown epoxy ink, and heated and cured at 70 ° C. for 1 hour to obtain a non-thermochromic image C Was formed. Next, using the heat-decolorable epoxy ink, cherry blossom leaves are printed on the tree branches of the non-thermochromic image C and cured by heating at 70 ° C. for 1 hour to form a reversible thermochromic image B. The reversible thermochromic image B
Next, cherry blossoms were printed using the above-described heat-coloring type epoxy ink, and were heated and cured at 70 ° C. for 1 hour to form a reversible thermochromic image A, thereby obtaining a reversible thermochromic mug.

In the reversible thermochromic mug, the reversible thermochromic image A (cherry blossom) is not visible in a room temperature environment, the non-thermochromic image C (tree pattern) and the reversible thermochromic image B (leaf pattern). Is visualized. When hot water of 60 ° C. is poured into the plastic cup, the reversible thermochromic image B is erased, and at the same time, the reversible thermochromic image A
The color develops, and the appearance of the flower blooming on the tree appears. Next, take out the warm water and leave the mug in a room temperature environment to return to the original design again. Incidentally, the aspect change due to the temperature change is repeatedly reproduced.

Example 4 Preparation of a reversible thermochromic pigment [(a) -4] A reversible thermochromic pigment [[a] -4] was prepared in the same manner as in Example 1 except that the reversible thermochromic composition (4) was used. (A) -4]
I got The reversible thermochromic pigment [(a) -4] is a heat-coloring type pigment, exhibits a discoloration behavior as shown in FIG. 1, is in a decolored state (colorless) in a normal temperature range, and becomes 33 when heated. ° C
Coloring starts near (T ₁ ), changes to a blue color developing state at 43 ° C. (T ₂ ), and when cooling is started, the color developing state is maintained up to 32 ° C. (T ₃ ) and gradually disappears by further cooling. It is completely decolored (T ₄ ) at 27 ° C.

Preparation of Reversible Thermochromic Pigment [(b) -3] A reversible thermochromic pigment [(b) -3] was prepared in the same manner as in Example 1 except that the reversible thermochromic composition (13) was used. 3]
I got The reversible thermochromic pigment [(b) -3] is a heat-decoloring type, and exhibits a discoloration behavior of coloring upon cooling (see FIG. 2). The color develops blue at 35 ° C. or lower, and decolors at 38 ° C. or higher. Presents a color (colorless) state.

Preparation of Ink 15.0 parts by weight of the reversible thermochromic pigment [(a) -4] was mixed with 15.0 parts by weight of a vinyl chloride-vinyl acetate copolymer resin, 2.0 parts by weight of an ultraviolet absorber, and cyclohexanone. 3
The mixture was uniformly dispersed and kneaded in a vehicle containing 5.0 parts by weight, 35.0 parts by weight of a high-boiling aromatic solvent, and 1.0 part by weight of an antifoaming agent to obtain a heat-colorable oil-based screen ink. In addition, a reversible thermochromic pigment [(b) -3] was used to form an ink with the same formulation as above to obtain a heat-decolorable oil-based screen ink.

Preparation of Reversible Thermochromic Display A message "High temperature" (reversible thermochromic image B) was formed on white synthetic paper by screen printing using the above-mentioned heated coloring oil-based screen ink. Next, a message of "suitable temperature" (reversible thermochromic image B) was formed adjacently using the above-mentioned heat-decolorable oil-based screen ink to produce a bath temperature checker.

In the bath temperature checker, the message of the reversible thermochromic image B “appropriate temperature” is always visually recognized in a bathroom or hot water of less than 40 ° C. Next, when the temperature of the bathroom or hot water reaches 43 ° C. or higher, the message of the reversible thermochromic image A “high temperature” appears and the message of “appropriate temperature” disappears. Next, when the checker was taken out of the bathroom or warm water and left in a room temperature environment, the checker returned to the original pattern. In addition, the above-mentioned aspect change due to the temperature change is repeated and reproduced.

Example 5 Preparation of Reversible Thermochromic Pigment [(a) -5] A reversible thermochromic pigment [[a] -5] was prepared in the same manner as in Example 1 except that the reversible thermochromic composition (5) was used. (A) -5]
I got The reversible thermochromic pigment [(a) -5] is a heat-colorable pigment, exhibits a discoloration behavior as shown in FIG. 1, is in a decolored state (colorless) in a normal temperature range, and becomes 30% when heated. ° C
Coloring starts around (T ₁ ), changes to a blue color developing state at 40 ° C. (T ₂ ), and when cooling is started, the color developing state is maintained up to 27 ° C. (T ₃ ) and gradually disappears by further cooling. It is completely decolored (T ₄ ) at 20 ° C.

Preparation of Reversible Thermochromic Pigment [(b) -4] A reversible thermochromic pigment [(b) -4] was prepared in the same manner as in Example 1 except that the reversible thermochromic composition (14) was used. 4]
I got The reversible thermochromic pigment [(b) -4] is a heat-decoloring type, exhibits a color-changing behavior of coloring upon cooling (see FIG. 2), develops an orange color at 31 ° C. or less, and decolors at 34 ° C. or more. Presents a color (colorless) state.

Preparation of Ink 40.0 parts by weight of the reversible thermochromic pigment [(a) -5) was added to an ethylene-vinyl acetate copolymer resin emulsion 50.
0 parts by weight, 3.0 parts by weight of an antifoaming agent, 1.0 part by weight of a thickener,
The mixture was uniformly mixed in a vehicle containing 3.0 parts by weight of a leveling agent to obtain a heat-colorable screen ink. In addition, a reversible thermochromic pigment [(b) -4] was used to form an ink according to the same formulation as above to obtain a heat-decolorable screen ink.

Production of Reversible Thermochromic Display A message of "hit" (reversible thermochromic image A) was formed on white high-quality paper by using the above-described heated coloring screen ink. Next, using a heating decoloring type screen ink,
An orange grid pattern (reversible thermochromic image B) was printed on the message to form a lottery.

In the lottery, a reversible thermochromic image B (lattice pattern) is visually recognized in a room temperature environment. Next, when the lattice pattern is heated by rubbing with a finger, the lattice pattern disappears and becomes a colorless state. When the lattice pattern is further heated to 40 ° C. or more by frictional heat, the reversible thermochromic image A
The message of "hit" appears. Next, when the lottery was left in a room temperature environment, it returned to the original design again. Incidentally, the aspect change due to the temperature change is repeatedly reproduced.

Example 6 Preparation of Reversible Thermochromic Pigment [(a) -6] A reversible thermochromic pigment [[a] -6] was prepared in the same manner as in Example 1 except that the reversible thermochromic composition (6) was used. (A) -6]
I got The reversible thermochromic pigment [(a) -6] is a heat-colorable pigment, exhibits a discoloration behavior as shown in FIG. 1, is in a decolored state (colorless) in a normal temperature range, and becomes 30% when heated. ° C
Coloring starts near (T ₁ ), becomes blue-green at 40 ° C. (T ₂ ), and when cooling is started, the color developing state is maintained up to 27 ° C. (T ₃ ). The color is erased and completely erased at 20 ° C. (T ₄ ).

Preparation of Reversible Thermochromic Pigment [(b) -5] A reversible thermochromic pigment [(b) -5] was prepared in the same manner as in Example 1 except that the reversible thermochromic composition (15) was used. 5]
I got The reversible thermochromic pigment [(b) -5] is a heat-decoloring type, exhibits a discoloration behavior that develops color upon cooling (see FIG. 2), develops a pink color at 30 ° C. or lower, and 32 ° C.
Above, it shows a decolored (colorless) state.

Preparation of Ink 15.0 parts by weight of the reversible thermochromic pigment [(a) -6] was added to 45.0 parts by weight of an acrylate resin emulsion, 3.0 parts by weight of a defoamer, and an alkali thickener. 5.0 parts by weight, 0.5 parts by weight of preservative, aqueous ammonia (35%)
The mixture was uniformly mixed in a vehicle containing 0 parts by weight to obtain a heat-colorable screen ink. In addition, a reversible thermochromic pigment [(b) -5] was used to form an ink according to the same formulation as above to obtain a heat-erasable screen ink.

Preparation of Reversible Thermochromic Display A blue-green dolphin pattern (reversible thermochromic image A) was formed on a white swimsuit by screen printing using the above-described heated coloring screen ink. Next, a tropical pink floral pattern (reversible thermochromic image B) was printed and formed on the reversible thermochromic image A using a heat-decolorable screen ink to produce a reversible thermochromic swimsuit.

The reversible thermochromic swimsuit has a tropical pink floral pattern in an indoor environment and in water.
In hot outdoor areas (sandy beach, beach side, etc.), the surface temperature of the swimsuit rises due to direct sunlight, and the floral pattern (reversible thermochromic image B)
Disappeared and a dolphin pattern (reversible thermochromic image A) appeared, and returned to the original tropical floral pattern in a room temperature environment or in water. In addition, the above-mentioned aspect change due to the temperature change is repeated and reproduced.

Example 7 Preparation of Reversible Thermochromic Pigment [(a) -7] A reversible thermochromic pigment [[a] -7] was prepared in the same manner as in Example 1 except that the reversible thermochromic composition (7) was used. (A) -7]
I got The reversible thermochromic pigment [(a) -7] is a heat-coloring type pigment, exhibits a discoloration behavior as shown in FIG. 1, is in a decolored state (colorless) in a normal temperature range, and becomes 33% when heated. ° C
Coloring starts near (T ₁ ), becomes blue-green at 43 ° C. (T ₂ ), and when cooling is started, the color developing state is maintained up to 32 ° C. (T ₃ ). The color is erased and completely erased at 27 ° C. (T ₄ ).

Preparation of reversible thermochromic pigment [(b) -6] A reversible thermochromic pigment [(b) -6] was prepared in the same manner as in Example 1 except that reversible thermochromic composition (16) was used. 6]
I got The reversible thermochromic pigment [(b) -6] is a heat-decoloring type, exhibits a discoloration behavior that develops color upon cooling (see FIG. 2), develops a pink color at 35 ° C. or lower, and 38 ° C.
Above, it shows a decolored (colorless) state.

Preparation of Resin Pellets 20.0 parts by weight of the reversible thermochromic pigment [(a) -7] and 20.0 parts by weight of the reversible thermochromic pigment [(b) -7] were mixed with a low-density polyethylene resin 1000. Parts by weight, UV absorber 1
After mixing in a mixture containing 0.0 parts by weight and 0.5 part by weight of a metal soap lubricant, uniformly dispersing with a tumbler mixer, melt-extrusion using an extruder, and reversible heat using a pelletizer. A discolorable polyethylene resin pellet was obtained.

Production of Reversible Thermochromic Display Molded Article A goldfish-shaped molded article was obtained from the reversible thermochromic pellet by blow molding using a goldfish mold.

The reversible thermochromic molded article (goldfish) has a pink color under a room temperature environment, but when immersed in warm water of 43 ° C. or more, the reversible thermochromic pigment [(b) -6] is formed. Decolorized and instantaneously turned colorless, but a reversible thermochromic pigment [(a)-
7] develops into a blue-green goldfish immediately, then is removed from warm water and left in a room temperature environment, or when immersed in water, the color gradually disappears and returns to the original pink goldfish. Is repeatedly reproduced.

Example 8 Preparation of ink 20.0 parts by weight of the reversible thermochromic pigment [(a) -2] and 20.0 parts by weight of the reversible thermochromic pigment [(b) -1] were mixed with a hard epoxy resin 60. 0.0 part by weight, 2.0 parts by weight of an ultraviolet absorber, 2.0 parts by weight of a thixotropic agent, and 1.0 part by weight of an antifoaming agent, and then uniformly dispersed and kneaded in a vehicle. 35.0 parts by weight of Group III polyamine was added, and the mixture was uniformly dispersed and kneaded to obtain a mixed color reversible thermochromic epoxy ink.

Preparation of Reversible Thermochromic Display A leaf design (non-thermochromic image C) was formed on the side of a ceramic mug using a green epoxy ink with a curved surface printing machine. Next, a floral pattern (reversible thermochromic mixed color image) was formed by printing using the mixed color reversible thermochromic epoxy ink.
In the mug, a blue flower pattern is visually recognized in a room temperature environment, and when the warm water of 60 ° C. is poured, the blue flower pattern disappears and immediately changes to a pink flower pattern. Then take out the hot water,
When the mug is left in a room temperature environment, the pink flower pattern disappears, becomes colorless, and then returns to a blue flower pattern. Incidentally, the aspect change due to the temperature change is repeatedly reproduced.

Example 9 Preparation of Reversible Thermochromic Pigment [(a) -9] A reversible thermochromic pigment [[a] -9] was prepared in the same manner as in Example 1 except that the reversible thermochromic composition (8) was used. (A) -9)
I got The reversible thermochromic pigment [(a) -9] is a heat-coloring pigment, exhibits a discoloration behavior as shown in FIG. 1, is in a decolored state (colorless) in a normal temperature range, and becomes 30% when heating is started. ° C
Coloring starts from near (T ₁ ), becomes pink at 42 ° C. (T ₂ ), and when cooling is started, the color developing state is maintained up to 28 ° C. (T ₃ ). The color is erased and completely erased at 20 ° C. (T ₄ ).

Preparation of Reversible Thermochromic Pigment [(b ')-9] A reversible thermochromic pigment [(b') was prepared in the same manner as in Example 1 except that the reversible thermochromic composition (17) was used. )-
9]. Said reversible thermochromic pigment [(b ')-9]
Is a heat-decoloring type that exhibits a decolored state in a room temperature environment (20-35 ° C.), and discoloration behavior that develops color upon cooling (FIG. 2)
), And develops a blue color at 10 ° C or lower, and exhibits a decolored (colorless) state at 16 ° C or higher.

Preparation of Ink 15.0 parts by weight of the reversible thermochromic pigment [(a) -9] was added to 45.0 parts by weight of an acrylate resin emulsion, 3.0 parts by weight of a defoamer, and an alkali thickener. 5.0 parts by weight, 0.5 parts by weight of preservative, aqueous ammonia (35%)
The mixture was uniformly mixed in a vehicle containing 0 parts by weight to obtain a heat-colorable screen ink. In addition, a reversible thermochromic pigment [(b ')-9] was used to form an ink according to the same formulation as above to obtain a heat-erasable screen ink.

Preparation of a reversible thermochromic display material A pink tropical hibiscus pattern (reversible thermochromic image A) on a light pink 50-denier polyester tricot fabric using the above-described heat-coloring type screen ink.
Was formed by screen printing. Next, a snow crystal pattern (reversible thermochromic image B ') is printed and formed on the reversible thermochromic image A using a heat-decolorable screen ink, and then cut and sewn to form a swimsuit for a reversible thermochromic doll. Was prepared.

The swimsuit for a reversible thermochromic doll has a pale pink state in an indoor environment (15 to 35 ° C.), and when cooled with cold water (about 10 ° C.), a blue-violet snow crystal pattern ( A reversible thermochromic image B ′) appears. Again under room temperature environment (about 25 ° C)
When left untreated, the snow crystal pattern disappears and returns to its original pale pink state. When heated with warm water (43 ° C.), a tropical hibiscus pattern (reversible thermochromic image A) appears,
When left in a room temperature environment, it returned to its original pale pink state.
In addition, the above-mentioned aspect change due to the temperature change is repeated and reproduced.

Example 10 Preparation of Reversible Thermochromic Pigment [(a) -10] A reversible thermochromic pigment [[a] -10] was prepared in the same manner as in Example 1 except that the reversible thermochromic composition (9) was used. (A) -1
0] was obtained. The reversible thermochromic pigment [(a) -10]
Is a heat-coloring type pigment, exhibits a discoloration behavior as shown in FIG. 1, is in a decolored state (colorless) in a normal temperature range, starts to color from about 30 ° C. when heating is started (T ₁ ), and is 42 ° C. in becomes blue colored state (T _2), then starts the cooling when 28 ℃
The color development state is maintained until (T ₃ ), and the color is gradually erased by further cooling to complete the color erasure state (T ₄ ) at 20 ° C.

Reversible thermochromic pigment [(b) -10],
Preparation of [(b) -11] and [(b ')-12] A reversible thermochromic pigment [(b) was prepared in the same manner as in Example 1 except that the reversible thermochromic composition (18) was used. -1
0] was obtained. Similarly, using the reversible thermochromic composition (19), the reversible thermochromic pigment [(b) -11], and using the reversible thermochromic composition (20), the reversible thermochromic pigment [(b ')-]. 1
2] was obtained. The reversible thermochromic pigment [(b) -10]
Is a heat-decoloring type that exhibits a color development state at room temperature, exhibits a discoloration behavior that develops color upon cooling (see FIG. 2), develops an orange color at 22 ° C. or lower, and decolorizes at 28 ° C. or higher (colorless) ) State. Reversible thermochromic pigment [(b) -1
1] is a heating and decoloring type which exhibits a colored state in a room temperature environment similarly to the above, and shows a discoloration behavior of being colored upon cooling (FIG. 2).
), And develops a black color at a temperature of 22 ° C. or lower and a colorless state at a temperature of 28 ° C. or higher. Reversible thermochromic pigment [(b ')
-12] is a heating-decoloring type that exhibits a decolored state in a room temperature environment (20-35 ° C.), exhibits a discoloration behavior that develops color upon cooling (see FIG. 2), and develops a pink color below 10 ° C. Above 16 ° C., a colorless state is exhibited.

Preparation of Ink and Preparation of Reversible Thermochromic Indicator 1.3 parts by weight of the reversible thermochromic pigment [(b) -10],
0.3 parts by weight of a reversible thermochromic pigment [(b) -11], 1.4 parts by weight of titanium oxide, 50.0 parts by weight of an acrylic resin xylene solution (50% solid content), 30.0 parts by weight of xylene,
A heating / decoloring type coating solution stirred and mixed in 20.0 parts by weight of a vehicle composed of 30.0 parts by weight of methyl isobutyl ketone is spray-coated on a soft vinyl chloride-vinyl acetate copolymer resin molded product by a spray gun. A reversible thermochromic image B of flesh color was provided. Next, on the reversible thermochromic image B, 5.0 parts by weight of the reversible thermochromic pigment [(b ')-12], 50.0 parts by weight of an acrylic resin xylene solution (solid content: 50%), and 30. 0 parts by weight, methyl isobutyl ketone 30.
A heating decoloring type coating solution obtained by stirring and mixing 0 parts by weight was spray-coated with a spray gun to provide a large number of small heart patterns (reversible thermochromic images B '). Further, on the reversible thermochromic image B ′, 5.0 parts by weight of a reversible thermochromic pigment [(a) -10],
A heating and coloring type coating liquid obtained by stirring and mixing 50.0 parts by weight of an acrylic resin xylene solution (solid content: 50%), 30.0 parts by weight of xylene, and 30.0 parts by weight of methyl isobutyl ketone,
A number of star patterns (reversible thermochromic images A) were provided by spray coating with a spray gun.

The molded body was placed in an indoor environment (15 to 35).
° C), a flesh color (reversible thermochromic image B) is shown, and when cooled with cold water (about 10 ° C), a pink heart pattern (reversible thermochromic image B ') appears. When left again in a room temperature environment (about 25 ° C.), the heart pattern disappears and returns to the original skin color.
On the other hand, when heated with warm water (43 ° C.), the color changed to a blue star pattern (reversible thermochromic image A), and when left in a room temperature environment, it returned to the original skin color. In addition, the above-mentioned aspect change due to the temperature change is repeated and reproduced.

Example 11 Preparation of Reversible Thermochromic Pigment [(a) -11] A reversible thermochromic pigment [[a] -11] was prepared in the same manner as in Example 1 except that the reversible thermochromic composition (10) was used. (A) -1
1] was obtained. The reversible thermochromic pigment [(a) -11]
Is a heat-coloring type pigment, exhibits a discoloration behavior as shown in FIG. 1, is in a decolored state (colorless) in a normal temperature range, starts to be colored from around 44 ° C. when heating is started (T ₁ ), and is 51 ° C. in becomes blue colored state (T _2), then starts the cooling the 33 ° C.
The color development state is maintained until (T ₃ ), and the color is gradually erased by further cooling to a completely erased state (T ₄ ) at 28 ° C.

Preparation of Reversible Thermochromic Pigment [(b) -13] A reversible thermochromic pigment [(b) -13] was prepared in the same manner as in Example 1 except that the reversible thermochromic composition (21) was used. 1
3] was obtained. The reversible thermochromic pigment [(b) -13]
Is a heating and decoloring type which exhibits a color developing state in a room temperature environment, exhibits a discoloration behavior of being colored upon cooling (see FIG. 2), develops a pink color at 22 ° C. or less, and decolors at 28 ° C. or more ( (Colorless) state.

Preparation of Ink and Preparation of Reversible Thermochromic Pigment 5.0 parts by weight of the reversible thermochromic pigment [(b) -13],
Acrylic resin xylene solution (50% solids) 45.0 parts by weight, xylene 15.0 parts by weight, methyl isobutyl ketone 25.0 parts by weight, polyisocyanate curing agent 6.0
The mixture was stirred and mixed in a vehicle consisting of parts by weight to obtain a heat-decolorable coating solution. The coating liquid was spray-coated on a miniature car made of ABS resin with a spray gun to form a pink color reversible thermochromic image B. Next, 5.0 parts by weight of the reversible thermochromic pigment [(b ')-9], 45.0 parts by weight of an acrylic resin xylene solution (solid content: 50%), and 15 parts of xylene.
In a vehicle consisting of 0 parts by weight, 25.0 parts by weight of methyl isobutyl ketone, and 6.0 parts by weight of a polyisocyanate-based curing agent, the mixture was stirred and mixed to obtain a heat-erasable coating liquid. The reversible thermochromic image B ′ was formed on the reversible thermochromic image B by spray coating with the coating liquid spray gun. Further, on the reversible thermochromic image B ′, a reversible thermochromic pigment [(a) -13]
5.0 parts by weight of an acrylic resin xylene solution (solid content 50
%) 45.0 parts by weight of xylene, 25.0 parts by weight of methyl isobutyl ketone, and 6.0 parts by weight of a polyisocyanate-based curing agent, were mixed with a vehicle by heating and using a heating and coloring type coating liquid. , "A" (reversible thermochromic image A) was spray painted.

The miniature car is operated in an indoor environment (15
(-35 ° C.), it exhibits a pink color (reversible thermochromic image B) and, when cooled with cold water (about 10 ° C.), changes to purple (reversible thermochromic image B ′). When left again in a room temperature environment (about 25 ° C.), the color returns from purple to the original pink color. On the other hand, when heated with warm water (52 ° C.), the pink color disappears and the blue alphabet letter A appears. When left in a room temperature environment again, it returned to the original pink miniature car. In addition, the above-mentioned aspect change due to the temperature change is repeated and reproduced.

[0069]

The reversible thermochromic display of the present invention has a constitution in which a heat-coloring type reversible thermochromic pigment and a heat-decoloring type reversible thermochromic pigment coexist. With this, various aspects can be hidden. Further, the reversible thermochromic pigment changes color at a temperature in a normal temperature range or a temperature near a normal temperature range, so that various aspects can be easily expressed. The display body described above is practically used in the form of a printed matter in which a plurality of print images are arranged, or in the form of a plastic molded body having multicolor discoloration, and has the taste of color change, unexpectedness, magic,
Satisfy the variety of designs.

[Brief description of the drawings]

FIG. 1 is a graph showing a temperature-color density curve of a heat coloring type reversible thermochromic composition applied to the present invention.

FIG. 2 is a graph showing a temperature-color density curve of a heat-decolorable reversible thermochromic composition applied to the present invention.

FIG. 3 is an explanatory diagram of an aspect before a change of an embodiment of the reversible thermochromic display of the present invention.

FIG. 4 is an explanatory diagram of a state after a change of the reversible thermochromic display of FIG. 3;

[Explanation of symbols]

REFERENCE SIGNS LIST 1 thermochromic display 2 support A thermochromic image containing reversible thermochromic pigment a B thermochromic image containing reversible thermochromic pigment b C non-thermochromic image T ₁ heat-coloring reversible thermochromic composition Color development start temperature T ₂ Complete color development temperature of heated color-forming reversible thermochromic composition T ₃ Decolorization start temperature of heated color-formed reversible thermochromic composition T ₄ Complete decolorization temperature of heated color-formed reversible thermochromic composition coloring initiation temperature of complete decoloring temperature t ₃ heat-decolorizable reversible thermochromic composition of the decoloring starting temperature t ₂ heated decolorizable reversible thermochromic composition of t ₁ heating decolorizable thermochromic composition complete coloring temperature t ₄ heating decolorizable thermochromic composition

Claims (9)

[Claims] 1. A thermochromic image A containing a reversible thermochromic pigment a that develops color by heating from a decolored state and is decolorized by lowering the temperature from the colored state, and decolorizes by heating from a colored state. A reversible thermochromic display 1 comprising a support 2 and a thermochromic image B containing a reversible thermochromic pigment b which develops a color when cooled from a state. 2. The reversible thermochromic display 1 according to claim 1, wherein the thermochromic image A and the thermochromic image B are arranged side by side or partially or entirely in an overprinted state. 3. A non-thermochromic image C is provided.
The reversible thermochromic indicator 1 according to the above. 4. The reversible thermochromic display 1 according to claim 1, wherein each of the thermochromic image A, the thermochromic image B, and the non-thermochromic image C is a printed image. 5. The reversible thermochromic display 1 according to claim 1, wherein the reversible thermochromic pigments a and b are blended to form a thermochromic mixed color image. 6. A reversible thermochromic pigment a, which forms a color by heating from a decolored state and decolors by cooling from the colored state;
A reversible thermochromic display 1 in which a reversible thermochromic pigment b, which is decolorized by heating from a color-developed state and is colored by cooling from the decolored state, is mixed and fixed in a dispersed state in a resin molded product. 7. In a normal temperature range (10 to 35 ° C.), the reversible thermochromic pigment a is in a decolored state, and the reversible thermochromic pigment b
The reversible thermochromic display 1 according to any one of claims 1 to 6, wherein is a colored state. 8. A color change temperature different from that of the reversible thermochromic pigment b, which is decolorized by heating from a color-developed state and colored by cooling from a decolored state, and decolorized in a normal temperature range (20 to 35 ° C.). The reversible thermochromic display according to any one of claims 1 to 7, wherein a reversible thermochromic image B 'including the reversible thermochromic pigment b' in a state is provided, or the reversible thermochromic pigment b 'is blended. One. 9. The reversible thermochromic pigment a includes (a) an electron-donating color-forming organic compound, (b) an alkoxyphenol compound represented by the following general formula (1) or a hydroxy compound represented by the following general formula (2). A microcapsule in which three essential components comprising an electron accepting compound selected from a benzoate compound and (c) a reaction medium for reversibly causing the electron transfer reaction according to the above (a) and (b) are encapsulated in a microcapsule. The reversible thermochromic display 1 according to any one of claims 1 to 8, which is a pigment. Embedded image (Wherein, R is a linear or branched alkyl group having 3 to 18 carbon atoms) (Wherein, R represents a straight-chain or side-chain alkyl group having 13 to 22 carbon atoms, and one or two of X, Y, and Z are hydroxyl groups;
The rest is hydrogen)